Reactions of Nickel(0)–Olefin Pincer Complexes with Terminal Alkynes: Cooperative C–H Bond Activation and Alkyne Coupling

María l. g. Sansores-Paredes, Tú t. t. Nguyen, Martin Lutz, Marc-Etienne Moret*

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

Metal-ligand cooperation can facilitate the activation of chemical bonds, opening reaction pathways of interest for catalyst development. In this context, olefins occupying the central position of a diphosphine pincer ligand (PC═CP) are emerging as reversible H atom acceptors, e.g., for H2 activation. Here, we report on the reactivity of nickel complexes of PC═CP ligands with a terminal alkyne, for which two competing pathways are observed. First, cooperative and reversible C-H bond activation generates a Ni(II) alkyl/alkynyl complex as the kinetic product. Second, in the absence of a bulky substituent on the olefin, two alkyne molecules are incorporated in the ligand structure to form a conjugated triene bound to Ni(0). The mechanisms of these processes are studied by density functional theory calculations supported by experimental observations.

Original languageEnglish
Pages (from-to)3418-3427
Number of pages10
JournalOrganometallics
Volume42
Issue number23
DOIs
Publication statusPublished - 11 Dec 2023

Keywords

  • Bond activation
  • Hydrocarbons
  • Ligands
  • Molecules
  • Solvents

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